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1. J. Bartl, S. Steenken, H. Mayr, and R. A. McClelland, J. Am. Chem. Soc. 112, 6918 (1990).
2. P. K. Das, Chem. Rev. 93, 119144 (1993).
3. R. A. McClelland, Tetrahedron 52, 68236858 (1996).
4. J. Ammer, C. F. Sailer, E. Riedle, and H. Mayr, J. Am. Chem. Soc. 134, 1148111494 (2012).
5. C. F. Sailer, S. Thallmair, B. P. Fingerhut, C. Nolte, J. Ammer, H. Mayr, I. Pugliesi, R. de Vivie-Riedle, and E. Riedle, ChemPhysChem 14, 1423 (2013).
6. J. Ammer and H. Mayr, J. Phys. Org. Chem. 26, 956969 (2013).
7. H. Mayr, Tetrahedron 71, 50955111 (2015).
8. H. Mayr and M. Patz, Angew. Chem., Int. Ed. 33, 938957 (1994).
9. H. Mayr, T. Bug, M. F. Gotta, N. Hering, B. Irrgang, B. Janker, B. Kempf, R. Loos, A. R. Ofial, G. Remennikov, and H. Schimmel, J. Am. Chem. Soc. 123, 95009512 (2001).
10. H. Mayr, J. Ammer, M. Baidya, B. Maji, T. A. Nigst, A. R. Ofial, and T. Singer, J. Am. Chem. Soc. 137, 25802599 (2015).
11. J. D. Coe, M. T. Ong, B. G. Levine, and T. J. Martínez, J. Phys. Chem. A 112, 12559 (2008).
12. J. González-Vázquez and L. González, ChemPhysChem 11, 36173624 (2010).
13. P. Krause and S. Matsika, J. Chem. Phys. 136, 034110 (2012).
14. M. Svensson, S. Humbel, R. D. J. Froese, T. Matsubara, S. Sieber, and K. Morokuma, J. Phys. Chem. 100, 1935719363 (1996).
15. S. Dapprich, I. Komáromi, K. Byun, K. Morokuma, and M. J. Frisch, J. Mol. Struct.: THEOCHEM 461–462, 121 (1999).
16. T. Vreven and K. Morokuma, J. Chem. Phys. 113, 2969 (2000).
17. M. J. Bearpark, S. M. Larkin, and T. Vreven, J. Phys. Chem. A 112, 7286 (2008).
18. S. Thallmair, M. Kowalewski, J. P. P. Zauleck, M. K. Roos, and R. de Vivie-Riedle, J. Phys. Chem. Lett. 5, 34803485 (2014).
19. S. Thallmair, J. P. P. Zauleck, and R. de Vivie-Riedle, J. Chem. Theory Comput. 11, 19871995 (2015).
20. K. S. Peters, Chem. Rev. 107, 859 (2007).
21. C. F. Sailer, N. Krebs, B. P. Fingerhut, R. de Vivie-Riedle, and E. Riedle, EPJ Web Conf. 41, 05042 (2013).
22. B. P. Fingerhut, D. Geppert, and R. de Vivie-Riedle, Chem. Phys. 343, 329 (2008).
23. L. E. Manring and K. S. Peters, J. Phys. Chem. 88, 35163520 (1984).
24. T. Bizjak, J. Karpiuk, S. Lochbrunner, and E. Riedle, J. Phys. Chem. A 108, 1076310769 (2004).
25. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, “Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2009” (2009).
26. H. Lischka, R. Shepard, I. Shavitt, R. M. Pitzer, M. Dallos, T. Müller, P. G. Szalay, F. B. Brown, R. Ahlrichs, H. J. Böhm, A. Chang, D. C. Comeau, R. Gdanitz, H. Dachsel, C. Ehrhardt, M. Ernzerhof, P. Höchtl, S. Irle, G. Kedziora, T. Kovar, V. Parasuk, M. J. M. Pepper, P. Scharf, H. Schiffer, M. Schindler, M. Schüler, M. Seth, E. A. Stahlberg, J.-G. Zhao, S. Yabushita, Z. Zhang, M. Barbatti, S. Matsika, M. Schuurmann, D. R. Yarkony, S. R. Brozell, E. V. Beck, J.-P. Blaudeau, M. Ruckenbauer, B. Sellner, F. Plasser, and J. J. Szymczak, “COLUMBUS, an ab initio electronic structure program, release 7.0” (2013).
27. M. R. Manaa and D. R. Yarkony, J. Chem. Phys. 99, 5251 (1993).
28. S. Matsika and D. R. Yarkony, J. Chem. Phys. 117, 6907 (2002).
29. M. Dallos, H. Lischka, R. Shepard, D. R. Yarkony, and P. G. Szalay, J. Chem. Phys. 120, 7330 (2004).
30. H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, M. Schütz, P. Celani, T. Korona, R. Lindh, A. Mitrushenkov, G. Rauhut, K. R. Shamasundar, T. B. Adler, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, E. Goll, C. Hampel, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Köppl, Y. Liu, A. W. Lloyd, R. A. Mata, A. J. May, S. J. McNicholas, W. Meyer, M. E. Mura, A. Nicklass, D. P. O'Neill, P. Palmieri, D. Peng, K. Pflüger, R. Pitzer, M. Reiher, T. Shiozaki, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, and M. Wang, “MOLPRO, version 2012.1, a package of ab initio programs” (2012).
31. M. J. Bearpark, M. A. Robb, and H. B. Schlegel, Chem. Phys. Lett. 223, 269274 (1994).
32. F. Eckert, P. Pulay, and H.-J. Werner, J. Comput. Chem. 18, 14731483 (1997).<1473::AID-JCC5>3.0.CO;2-G
33. F. Sicilia, L. Blancafort, M. J. Bearpark, and M. A. Robb, J. Chem. Theory Comput. 4, 257266 (2008).
34. H.-J. Werner and W. Meyer, J. Chem. Phys. 74, 5802 (1981).
35. A. J. Dobbyn and P. J. Knowles, Mol. Phys. 91, 1107 (1997).
36. E. S. Kryachko and D. R. Yarkony, Int. J. Quantum Chem. 76, 235 (2000).<235::AID-QUA12>3.0.CO;2-Y
37.See supplementary material at for the two-dimensional diabatic PES of diphenylmethylchloride (Fig. S1), details of the QD simulations, and optimized geometries.[Supplementary Material]
38. H. Tal-Ezer and R. Kosloff, J. Chem. Phys. 81, 3967 (1984).
39. B. Podolsky, Phys. Rev. 32, 812 (1928).
40. E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra ( Dover Publications, New York, 1980).
41. L. Schaad and J. Hu, J. Mol. Struct.: THEOCHEM 185, 203 (1989).
42. B. P. Fingerhut, C. F. Sailer, J. Ammer, E. Riedle, and R. de Vivie-Riedle, J. Phys. Chem. A 116, 1106411074 (2012).
43. S. Thallmair, B. P. Fingerhut, and R. de Vivie-Riedle, J. Phys. Chem. A 117, 1062610633 (2013).
44. Y. Zhao and D. Truhlar, Theor. Chem. Acc. 120, 215241 (2008).
45. S. Thallmair, M. K. Roos, and R. de Vivie-Riedle, “ The design of specially adapted reactive coordinates to economically compute potential and kinetic energy operators including geometry relaxation” (unpublished).

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Photoinduced bond cleavage is often employed for the generation of highly reactive carbocations in solution and to study their reactivity. Diphenylmethyl derivatives are prominent precursors in polar and moderately polar solvents like acetonitrile or dichloromethane. Depending on the leaving group, the photoinduced bond cleavage occurs on a femtosecond to picosecond time scale and typically leads to two distinguishable products, the desired diphenylmethyl cations (PhCH+) and as competing by-product the diphenylmethyl radicals (). Conical intersections are the chief suspects for such ultrafast branching processes. We show for two typical examples, the neutral diphenylmethylchloride (PhCH–Cl) and the charged diphenylmethyltriphenylphosphonium ions () that the role of the conical intersections depends not only on the molecular features but also on the interplay with the environment. It turns out to differ significantly for both precursors. Our analysis is based on quantum chemical and quantum dynamical calculations. For comparison, we use ultrafast transient absorption measurements. In case of PhCH–Cl, we can directly connect the observed signals to two early three-state and two-state conical intersections, both close to the Franck-Condon region. In case of the , dynamic solvent effects are needed to activate a two-state conical intersection at larger distances along the reaction coordinate.


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